Process for manufacturing bleaching compositions comprising chlorine and bromine sources and product thereof

ABSTRACT

An improved process for the manufacture of alkaline bleaching compositions, especially liquid and/or gel compositions of high solubility and low abrasiveness, useful to the consumer, especially as products for hard surface cleaning, bleaching or disinfectancy. The products are made by a three-stage process and comprise particular chlorine and bromine bleach sources and particular aminofunctional materials such as low-impurity sulfamate. The process has mixing sequences and starting ingredient selections which provide unexpectedly improved product

FIELD OF THE INVENTION

The present invention relates to a process for the manufacture ofalkaline bleaching compositions useful to the consumer, especially asproducts for hard surface cleaning, bleaching or disinfectancy. Theproducts comprise both chlorine and bromine bleach sources. The processhas mixing sequences and starting ingredient selections which provideunexpectedly improved product.

BACKGROUND OF THE INVENTION

Hard surface cleaners, bleaches and disinfectants are well knownformulated consumer products. They are useful for treating all manner ofsoiled kitchen, bathroom, sink, tub, shower, toilet bowl and counter topsurfaces.

Such consumer products are known to include hypochlorite bleach.Hypochlorite is desirable for its high effectiveness as a bleach anddisinfectant. However, it has several disadvantages, including that itcan sometimes be too aggressive, tends to leave an unpleasant odor onthe hands, and is not always stable on storage in a consumer productformulation.

Bromine containing compounds have been used in specialized circumstancesfor bleaching or disinfectancy. However they tend to be expensive andare often even more demanding in terms of storage stability than thechlorine analogs.

Sulfamic acid has been used as a cleaner, especially in acidic cleanersdelivering high concentrations of the acid.

The chemistry of sulfamate-containing systems with halogens isextraordinarily complex and research in this area continues to this day.

Despite the partly known features of the art, there is an ongoing needfor hard surface cleaners, bleaches and disinfectants suitable forconsumer use which are improved in one or more of their characteristicsincluding having superior effectiveness as a bleach and disinfectant,being less aggressive, tending to leave very low odor or even pleasantodor on the hands, and being highly stable on storage.

Accordingly, an improved process for making such compositions isprovided herein, and the alkaline bleaching compositions securedthereby.

The process herein has several advantages, including that it is easy tooperate and is safe and effective for its intended purpose.Surprisingly, it delivers a product which is actually superior to theproduct which is achieved when numerous other mixing sequences areemployed.

BACKGROUND ART

Commonly assigned U.S. Pat. No. 3,583,922, Mc Clain and Meyer, Jun. 8,1971 and Canadian Patent Publ. CA 860279 A, published Jan. 5, 1971describe a solid composition for rapid removal of tannic acid stainshaving pH not less than 10.5 consisting of 0-95% abrasive, up to 10%surfactant, 0-60% alkaline builder, a stable compound, preferablychlorinated trisodium orthophosphate, to provide 0.5%-5% availablechlorine, sulfamic acid to produce preferably a ratio of Cl to sulphamicadd of 500 to 1:1, preferably 3:1 to 6:1, optionally with additives.Such additives can include bromides, perfumes or borax. The compositionscan be adjusted for sink cleaning or mechanical dish washing.

JP 63108099 A, Lion Corp., published May 12, 1988 describes a bleachingagent for controlling chlorine odor containing a specific ratio ofhypochlorite and sulfamic acid and/or sulfamate and pH adjusting agents.The ratio is 2-8 wt% hypochlorite based on "the amount of the effectivechlorine" (sic) and there is a 0.25 to 1.5 mol ratio of sulfamic acid,and/or a sulfamate, to hypochlorite.

JP 63161088 A, Lion Corp., published Jul. 4, 1988 describes bleachingcompositions for cloth comprising mainly hydrogen peroxide and sulfamicacid and/or water-soluble sulfamate and hypohalous acid and/or awater-soluble hypohalite salt such as NaClO, Ca(OCl)₂, bleaching powderor NaBrO, the sulfamate being present in an amount of 0.5-5 mol per molhypohalite.

U.S. Pat. No. 4,992,209, Feb. 12, 1991, Smyk et al describes abactericidal, fungicidal system having a nitrite-containing corrosioninhibitor, for example cooling systems, prepared by reacting NaBr withNaOCl or Cl₁₂ and sodium sulfamate or sulfamic acid and the product isassertedly "reacted within 5 hours of preparation".

U.S. 5,431,839, Guillou, Jul. 11,1995 describes sulfamic acidcleaning/stripping compositions comprising heteropolysaccharidethickening agents. U.S. Pat. No. 5,047,164, Sep. 10, 1991, Corby,describes compositions containing interhalogens and acid especiallyadapted for cleaning and disinfecting milk- and food-handling equipment.U.S. Pat. No. 4,279,764, Brubaker, Jul. 21, 1981 describes encapsulatedbleaches comprising storage stable chlorinated isocyanurates. U.S. Pat.No. 4,233,173, Mayer et al, Nov. 11, 1980 and U.S. Pat. No. 4,201,687,Crutchfield et al describe detergent compositions containingchloroimidodisulfate bleaching agent. U.S. Pat. No. 5,470,499, Choy etal, Nov. 28, 1995 describes thickened aqueous abrasive cleansers withimproved rinsability. Commonly assigned U.S. Pat. No. 4,051,056, Sep.27, 1977, Hartman describes abrasive scouring compositions with perliteand hypochlorite bleach. Commonly assigned U.S. Pat. No. 3,715,314,Morgenstern, Feb. 6, 1973 describes scouring cleanser compositions.Commonly assigned U.S. Pat. No. 5,384,061, Wise, Jan. 24, 1995 describesstable thickened aqueous bleaching compositions comprising chlorinebleach and phytic acid. Industrial uses of sulfamic acid are included ina literature review, see "Inorganic Sulfur Chemistry", G. Nickless, Ed.,Elsevier, 1968, Chapter 18, "Amido- and Imido-sulphonic acids", 607-667and references cited therein; see also Kirk Othmer Encyclopedia ofChemical Technology, 3rd Ed., Wiley-Interscience, Vol. 21, "SulfamicAcid and Sulfamates", pp 949-960. Chloramines, Bromamines andN-halamines more generally are reviewed in Kirk Othmer's Encyclopedia ofChemical Technology, Wiley-Interscience, 4th Ed., Vol. 5, pp 911-932;see also a corresponding article in the 3rd edition of the sameEncyclopedia. Chlorine gas has previously been mixed with solutionscontaining sulfamic acid: see Korshak et al., Zh. Obsch. Khim., Vol. 18(1948), pages 753-756, but the mixture decomposed.

SUMMARY OF THE INVENTION

The present invention encompasses a process for manufacturing analkaline bleaching composition, preferably an aqueous liquid bleachingcomposition, said process comprising at least three stages. These stagesinclude, in sequence (I) a pre-bromine stage, (II) a bromine compoundaddition stage, and (III) a product stabilization stage, and each ofsaid stages has at least one mixing step.

In said process, said pre-bromine stage, (I), comprises a step, (a), ofmixing in any order components comprising a hypochlorite source and anaminofunctional compound having a stable N-halo derivative; therebyforming a stage (I) mixture; provided that at the end of saidpre-bromine stage, said stage (I) mixture has a pH not exceeding about11, preferably lower; said bromine compound addition stage, (II), isInitiated at said pH and comprises a step, (b), of mixing in any orderwith said stage (I) mixture, a bromine compound; thereby forming a stage(II) mixture; and said product stabilization stage, (III), comprises atleast one step, (c), of mixing in any order with said stage (II)mixture, an alkali in an amount suitable to arrive at a final pH for theproduct of said process of at least about 13.

The product provided by this process has unique advantages in terms ofexcellent bleaching effect at the same time as permitting a minimizationof "bleach odor" on skin. The preferred product is a transparent yellowaqueous liquid, which may optionally be thickened and/or perfumed.

All percentages, ratios, and proportions herein are on a weight basisunless otherwise indicated. All documents cited are hereby incorporatedby reference in their entirety.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 represents a schematic outline of the present process, showingthe conversion of starting-materials (ingredients) to product via aseries of stages, comprising, in sequence, Stage (I), Stage (II) andStage (III). Each stage, as indicated, includes one or more steps. Stage(I) includes an essential step, namely Step (a). Stage (II) includes anessential step, namely Step (b), and Stage (III) includes an essentialStep, namely step (c). The present process in the most reduced formwhich can be constructed from FIG. 1 consists of the sequence of threesteps (a) followed by (b) followed by (c). Each of the essential stagesand steps, as well as suitable ingredients and characteristics of theproduct are described in detail hereinafter.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, it has been discovered that inorder to secure an alkaline bleaching composition having superiortechnical performance and desirability for the consumer, it is necessaryto provide two distinct types of halogen ingredient including at leastone having, at the outset, the form of a bromine compound and at leastone having, at the outset, the form of a hypohalit compound. It has alsobeen found essential to particularly select and include a certainaminofunctional compound; and to provide a particular process,especially in terms of mixing sequence, to secure the product benefits.

Alkaline Bleaching Compositions

Accordingly, the present invention relates to processes for makingalkaline bleaching compositions and to the products thereof. "Alkalinebleaching compositions" as defined herein are strongly alkaline. The"alkaline bleaching compositions" herein have a pH as is of at leastabout 13, and are made from ingredients comprising a hypophalite soureand a bromine compound along with at least one particularly selectedaminofunctional compound. Alkaline beaching compositions herein areuseful to the consumer as products for hard surface cleaning, bleachingor disinfectancy. They can, in general, have any suitable physical form,such as granular, tablet, paste, gel or liquid form, and can be aqueousor non-aqueous. However, the process herein is especially well adaptedfor making aqueous, alkaline, liquid-form or gel-form bleachingcompositions: technical problems of processing are greatest for suchcompositions. Unless otherwise noted, embodiments hereinafter whichillustrate the processes and product of the invention therefore relateto the aqueous liquid forms.

Process Stages

Processes herein generally comprise at least three stages:

(I) a pre-bromine stage;

(II) a bromine compound addition stage, and

(III) a product stabilization stage.

The stages are carried out in the order (I) then (II) then (III). Thestages are identified in FIG. 1. Each stage includes one or more steps.In a minimum configuration, the process includes, in Stage (I), step(a); in Stage (II), step (b), and in Stage (III), step (c). Additionalsteps, for example of adding and/or mixing other ingredients such asperfumes, surfactants and the like, may be inserted before or after anyof the essential steps, provided that they do not affect the indicatedsequence of essential steps and further, that they are perfomedcompatibly with respecting the pH criticalities described herein.

In more detail, Stage (I), the pre-bromine addition stage, is a stageused to bring together a hypochlorite source and a particularaminofunctional compound; Stage (II), the bromine compound additionstage, is a stage used to introduce a bromine compound; and stage (III),the product stabilization stage, is a stage used to stabilize theproduct by increasing pH.

Thus the invention encompasses a process for manufacturing an alkalinebleaching composition, said process comprising at least three stagesincluding, in sequence, (I) a pre-bromine stage, (II) a bromine compoundaddition stage, and (III) a product stabilization stage, each of saidstages having at least one mixing step; wherein in said process, saidpre-bromine stage comprises a step, (a), of mixing in any ordercomponents comprising a hypochlorite source and an aminofunctionalcompound having a stable N-halo derivative; thereby forming a stage (I)mixture; provided that at the end of said pre-bromine stage, said stage(I) mixture has a pH not exceeding about 11; said bromine compoundaddition stage is initiated at said pH and comprises a step, (b), ofmixing in any order with said stage (I) mixture, a bromine compound;thereby forming a stage (II) mixture; and said product stabilizationstage comprises at least one step, (c), of mixing in any order with saidstage (II) mixture, an alkali in an amount suitable to arrive at a finalpH for the product of said process of at least about 13.

Particularly preferred processes herein are restrictive in terms of whenthe bromine compound may be added. In preferred processes, no stageother than (II) and no step other than (b) comprises adding a brominecompound. Surprisingly, it has been found that adding bromine compoundelsewhere in the sequence has a negative impact on product performance.

Optional Process Steps

The present process can include various optional steps. An optional stepuseful herein is illustrated by a dilution step, included in the processafter completion of stage (III). Such a step as a dilution step can infact be carried out either by the manufacturer, or by the user of theproduct of stages (I), (II) and (III). Dilution steps can in general beincluded in stage (I), stage (II) or stage (III) of the present process,though prefereably, dilution is avoided in those stages. Typically forbest storage stability, a dilution step is not carried out in the plant,but rather, by the consumer who uses the composition. Dilution canresult in pH variation, typically including pH decrease. Other optionalsteps useful herein include surfactant addition steps, or steps ofadding or mixing any suitable optional ingredient, such as thoseidentified under "optional ingredients" hereinafter.

Process Means

Any suitable means may be employed for accomplishing the presentprocess. Reactors are desirably chemically inert to halogen bleach andstrongly alkaline conditions, plastics and/or borosilicate glass linedapparatus is desirably used both for durability and to minimizecontamination of the product by metals. Reactors need not be designedfor operation under pressure provided that suitable venting is provided.Mixing of ingredients can be accomplished using any suitable mixer, suchas a motor-driven paddle. Alternately, a centrifugal pump can be used toprovide a recirculating jet of product solution, driving agitation ofthe mixture. Other useful process means herein include means forremoving vapors from the work environment. Such means includeconventional scrubbers, etc.

Process Conditions

Temperature

In general the present process can be carried out at widely rangingtemperatures. Preferably, each of said steps (b) and (c) is performed ata temperature in the range from about 5° C. to about 80° C., preferablyfrom about 10° C. to about 45° C., most preferably at or about ambienttemperature, e.g., about 20° C. Highly preferred process hereinaccomplish all steps in stages (I), (II) and (III) at such temperatures.At higher temperatures, there may be an increased decomposition tendencyand at lower temperatures, freezing can be a problem.

pH's

The present process requires particular limits on pH variation. There isa general requirement that at the end of the pre-bromine stage and atthe beginning of the bromine stage, the pH of the stage (I) mixture isnot in excess of about 11. In preferred embodiments, this pH is not inexcess of about 8, more preferably, it lies in the range from about 1 toabout 6.9.

In preferred embodiments, from the end of stage I, the entire process isconducted at a rising pH. Such rising pH desirably corresponds with avalue of dpH/dt of at least about +0.1 pH units/min, preferably about+0.5 pH units/min, or higher.

In such embodiments, it will be appreciated that the instant processcontains a pH minimum. The position in the overall sequence of thepresent process of this minimum is found at the end of stage (I).

Pressure

The present process can be conducted at any convenient pressure. Forexample, chlorine gas and alkali can be reacted under pressure, forexample up to about 5 atm., in stage (I) prior to adding theaminofunctional compound; and the following stages of the process can beconducted at atmospheric pressure, or even at reduced pressure ifscrubbers or condensers are provided for collecting lost halogen.Preferred processes are conducted at atmospheric pressure.

Time

The present process can be conducted in batch or continuous mode. Unlessotherwise indicated, illustrations of the process hereinafter arebatch-mode. Times for completion of a batch may in general vary widely.Typically, times of about 5 min to about 1.5 hours are typical for eachof stages (I), (II) and (III). In preferred embodiments, Stage (II) willallow at least sufficient time to permit the bromine compound tosubstantially dissolve before proceeding with stage (III). Alsopreferably, stage (II) is continued until development of a yellow colorin the stage (II) mixture. In general, the longer process times areassociated with larger-scale processes. It is preferred herein tominimize the overall reaction time, and in particular, while allowingsufficient time for stage (II), to proceed without delay from that stageto the end of stage (III). Moreover, it is highly preferred to minimizeany time period between the end of step (a) and the beginning of step(b), and between the end of step (b) and the beginning of step (c).

Concentration and Concentration Ratios

The present process can be conducted over a wide range of concentrationsof the ingredients in water. In preferred embodiments, the process ischaracterized by a dilution factor for the sum of stages subsequent tostage (I) which is not in excess of about twofold. In general,concentrations of the ingredients are adjusted such that the product ofstage (III), comprises from about 0.01% to about 10% Available Chlorine.Also, in terms of relative proportions of the ingredients, the presentprocess preferably relies on an interhalogen ratio [Br] : [OCI⁻ ] offrom about 10: 1 to about 1: 10, preferably 1:2 to 1:5, wherein [Br]represents total moles Br added into said process from said brominecompound and [OCI⁻ ] represents total moles hypochlorite added into saidprocess from said hypochlorite source. Moreover, the preferred processesherein employ an amino-halo ratio [A]: [X] of from about 10: 1 to about1: 10, wherein [A] represents the total of moles of amino moieties ofsaid aminofunctional compound used to form said composition and wherein[X] represents total moles of bleaching halogen, measurable as AvailableChlorine, added into said composition.

Very preferably, said amino-halo ratio is from about 1.0: 1.0 to about1.5: 1.0.

To illustrate, with respect to the above quantities, sulfamic acid,which contains one mole of amino moieties per mole of the compound, iseasily computed in the above relation: [A] is simply the number of molesof sulfamate; but to give another illustration, when melamine is used,[A] is the number of moles of melamine used multiplied by the number ofmoles (which is 3) of amino moieties contained in any one mole ofmelamine.

Ingredients

Hypochlorite Source

In general, any convenient hypochlorite source can be used in theinstant process. Preferred hypochlorite sources are selected fromchlorine, hypochlorous acid, alkali metal hypochlorites, alkaline earthmetal hypochlorites, the product of mixing a hypochlorite-liberatingcompound with aqueous alkali, and mixtures thereof. Suitablehypochlorite-liberating compounds, in the sense immediately above, areillustrated by dichloroisocyanuric acid and its sodium salts andhydrates, which hydrolyze rather readily to release hypochlorite. Highlypreferred hypochlorite sources herein are selected from alkali metalhypochlorites and the product of mixing said hypochlorite-liberatingcompound and aqueous alkali.

Aminofunctional compound

From the thousands of available aminofunctional compounds, the presentinvention selects a limited few which are found operative. In processesof the invention, suitable aminofunctional compounds are those havingstable N-halo derivatives. The term "having a stable N-halo derivative"herein is defined as "capable of forming an N-halo derivative and it isstable", rather than as necessarily "possessing a stable N-halo moietyat the inception of the present process". Suitable aminofunctionalcompounds meeting the needs of the present invention are selected from(i) primary aminofunctional compounds selected from sulfamic acid,alkali-metal sulfamates, alkaline earth sulfamates, tetra-alkylammoniumsulfamates, and mixtures thereof; (ii) secondary aminofunctionalcompounds selected from secondary amine derivatives having formula RR'NHor (R")₂ NH wherein R, R' and R" are organic moieties and wherein carbonatoms of said organic moieties are bonded covalently to NH; (iii)sulfonamides selected from sulfamide, p-toluenesulfonamide,imidodisulfonamide, benzenesulfonamide, alkyl sulfonamides, and mixturesthereof; (iv) melamine, cyanamide; and (v) mixtures thereof.

Suitable secondary aminofunctional compounds (ii) include those notspecifically identified in (i), (iii), (iv) and (v), wherein R, R' andR" are independently selected from C1-C12 linear saturated and C3-12branched saturated moieties which can be alkyl, aryl or heterocyclic,optionally substituted by carboxylic acid or carboxylate: an example ofthe latter carlxylic-substituted derivatives is thealpha-aminobutyrates. Preferred secondary aminofunctional compounds areknown for use as disinfectants, especially those which are water-solubleand those having N-halo derivatives which are relatively insensitive toshock.

In alternate terms, the present process is believed to be applicablewherever the aminofunctional compound has a hydrolysis constant, K, asdefined by

    K=[HOCI][RNH.sub.2 ] / [RNHCI]

    or K=[HOCI][RR'NH] / [RR'NCI]

    or K=[HOCI][(R").sub.2 NH] / [(R").sub.2 NCI]

in the range of from about 10⁻⁶ to about 10⁻⁹, provided that noisocyanurate or chlorinated isocyanurate is included as the essentialaminofunctional compound.

Hydrolysis constants such as the above are well known in the art and aredefined conventionally. See, for example, Kirk Othmer's Encyclopedia ofChemical Technology, 3rd Ed., Vol. 5, article entitled "Chloramines andBromamines", see especially page 567, and Kirk Othmer's Encyclopedia ofChemical Technology, 3rd Ed., Vol. 3, see especially pages 940-941,these articles being incorporated herein by reference.

Subject to the above-identified requirements, preferred secondaryaminofunctional compounds can be selected from those identified in KirkOthmer, Encyclopedia of Chemical Technology, 4th. Ed., 1993, pages918-925 and include compounds identified under the headings "OrganicChloramines and Bromamines", "Aliphatic Compounds", "Aromatic Compounds"and "Heterocyclic Compounds".

Sulfamic acid or sodium sulfamate are highly preferred aminofunctionalcompounds herein.

Alkali

Suitable alkali in the present process is selected from alkali-metal-,alkaline-earth-, and tetraalkylammonium- oxides, hydroxides, carbonates,bicarbonates, silicates, phosphates, borates, and mixtures thereof.

Bromine compound

Suitable bromine compounds in the present process are selected from thegroup consisting of bromine, water-soluble bromide salts, water-solublehypobromite salts, hypobromous acid, and mixtures thereof.

Overall Preferred Combinations of Ingredients

In an overall preferred process herein, said hypochlorite source isselected from alkali metal hypochlorites and the product of mixing ahypochlorite-liberating compound and aqueous alkali; saidaminofunctional compound is selected from sulfamic acid, alkali-metalsulfamates, alkaline earth sulfamates, tetra-alkylammonium sulfamates,and mixtures thereof; and said bromine compound is selected from thegroup consisting of water-soluble bromide salts. Highly preferred hereinis a process wherein said hypochlorite source is sodium hypochlorite,said aminofunctional compound is sulfamic acid; and said brominecompound is selected from sodium bromide, potassium bromide and mixturesthereof.

Ingredients or Impurities Desirably Excluded

The present process and product thereof preferably limits certaincompounds which have been found to adversely affect product stabilityand effectiveness. Especially undesirable compounds herein are thoseaminofunctional compounds which do not form stable N-halo derivatives.Such compounds include simple ammonium (NH₄ ⁺) salts, such as ammoniumsulfate; urea; amino acids such as aspartic acid; and mixtures thereof,any of which may, for example, produce unpleasant odors of undesirablechloramines. Preferred herein are processes wherein throughout, and atleast in the essential aminofunctional compound, no ingredient comprisesmore than about 1% of aminofunctional impurity compounds having unstableN-halo derivatives. Translating this requirement in practical terms,sulfamic acid is commercially available in a range of grades, certain ofwhich may include urea as an impurity.

The crystal grade of sulfamic acid, which minimizes urea impurity, isfound to be preferred. In other process embodiments, the present processis conducted using starting materials which are all water-soluble thatis to say, excluding insoluble materials such as abrasives, therebyavoiding any tendency for surface-catalyzed bleach decomposition.

Acids and Bases for pH Adjustment

Any convenient alkali or base can be used herein as a pH-adjusting agentfor increasing pH, and any convenient acid can be used herein as apH-adjusting agent for decreasing pH; always provided that such alkalior acid is non-reactive with hypohalite. Preferred alkalis for pHadjustment include water-soluble alkalis such as sodium hydroxide,potassium hydroxide or mixtures thereof, and preferred acids include thecommon mineral acids such as sulfuric, hydrochloric or nitric, thoughsulfuric is preferred in this group. Alternately relatively weak addscan be used; these include acetic acid.

Examples of bases which knowledgeable practitioners will avoid entirelyin the present process include ammonia because it is chemically reactivewith other essential ingredients herein for purposes other than pHchange, forming, for example, an undesirable type of chloramine when itreacts with hypochlorite.

In general, any simple mineral acid or base additions in the presentprocess will be carried out in a manner consistent with preserving thechemical integrity of the aminofunctional compound. For example, whenusing sulfamic acid as the aminofunctional compound, mineral acidadditions are conducted under sufficient dilution to avoid decompositionof the sulfamic acid. Concentrated nitric acid, for example, is known todecompose sulfamic acid at HNO₃ concentrations of 73%, especially atelevated temperatures, with formation of nitrous oxide, and suchcombination of concentrated mineral acid and elevated temperature isavoided in the instant process.

Water

Water used for making liquid compositions according to the presentprocess is suitably city water. In general, hard, soft, softened ordeionized water may be used. Distilled or reverse-osmosis treated waterare especially desirable. When using water of uncertain quality, forexample ferruginous water or high-manganese water from boreholes, it isdesirable to reduce the dissolved metal content by conventional watertreatment approaches, for example, oxygenation, filtration, andsettling. Moreover a chelant or sequestrant can be used to treat processwater. It is prudent to monitor or periodically check, and if needed,minimize transition metal ion content of the water by conventionaltechniques since transition metal ions are well known to affect bleachproduct stability. Suitable analysis is by atomic absorptionspectroscopy or inductively coupled plasma spectroscopy (ICP).

pH Measurement

pH herein is measured using a glass electrode or combination electrodesuch as Coming General Purpose Combination electrode Cat. No. 476530,and a commercial pH meter such as the Φ 40 pH meter available fromBeckman.

pH Ramping

It is desirable, and indeed characteristic of the present process asbest currently known, for there to be present a downward pH ramp (a"ramp" herein being a relatively linear increase or decrease in pH withtime) followed by an upward pH ramp, there being a strong minimum in thepH as indicated in the process definition. In the latter part of theprocess, as noted hereinabove, the upward ramp of pH, measurable bydpHldt, is specifically in a defined range believed to be linked tostability and performance.

Bleach ingredient measurement: Available Chlorine

The term "Available Chlorine" sometimes abbreviated "AvCl₂ " as usedherein is described in Kirk Othmer's Encyclopedia of ChemicalTechnology, Vol. 4, 4th Ed. (1992) pages 274-275 published byWiley-Interscience.

Reactions which produce an oxidant from chlorine include the following:##STR1##

The total concentration or amount of any given chlorine-based oxidant isoften pressed on an equivalent basis, as though all the oxidant werechlorine. Available Chlorine is thus the equivalent concentration oramount of chlorine needed to produce an oxidant, for example accordingto the above reactions, and can be measured by conventional measures,such as iodometric methods referenced in Kirk-Othmer (op. cit).

Available Chlorine can be calculated from the following relation:

    Available Chlorine (%)=70.9× moles of oxidant× (number of active CI atoms / molecule)×100

In the above relation, the term "active Cl atoms" needs definition:Because Cl₂ only accepts two electrons, as does HOCI andmonochloroamines, it has only one "active" Cl atom according to thepresent definition.

When determining the Available Chlorine expected for product of theinstant process, "moles of oxidant" in the above relation is replaced by"total moles of bleaching halogen added in forming the composition".

Note that "Available Chlorine" can be determined for bleaches that donot actually form hypochlorite in solution, such as bromine-containingbleaches, and other nonchlorine bleaches, by substituting the number ofelectrons accepted divided by two for the number of active chlorineatoms in the above relation. This can also be measured by iodometrictitration.

Note also that the Available Chlorine unit is a dimensionlesspercentage, not a percentage by weight. It should be apparent from thedefinition that it is in fact possible in general terms to obtainAvailable Chlorine values which exceed 100%; this can happen in the caseof a chlorine bleach which is more mass efficient than Cl₂, recallingthat only one chlorine atom in Cl₂ is a bleaching chlorine atom;however, such levels are not encountered in the present process.

Amounts and Ratios of ingredients

In general, amounts and aqueous concentrations of ingredients herein mayvary quite widely; nonetheless there is a strong preference forparticular interhaogen ratios as defined elsewhere herein and it iscommercially attractive to use ingredients such as sodium hypochloriteat the most economic concentrations provided by their manufacturers.

Advantages

As noted, the present invention has significant advantages, for exampleimproved bleaching. By "improved bleaching" it is meant herein that acomposition obtainable with the process of the present inventiondelivers better bleaching performance on bleachable stains like teastains, as compared to the bleaching performance delivered by the samecomposition made by another process, for example one involving numerousalternate orders of addition or mixing of the ingredients. Importantly,concurrent with improved bleaching, the formulations provided by theprocess leave low residual odor on skin and are milder than thoseotherwise manufactured with different ingredient selections and/ororders of addition. In short the combination of overall performance anddesirable skin safetylaesthetics offered by the present process arebelieved to be measurably superior to those attainable by anyart-recognized process.

Product Characteristics

The product of the present process is not in general limited as to form,though it is highly preferred for the compositions produced to beaqueous liquids or aqueous gels. Another product form potentiallypreferred herein is a "high-solubility solid concentrate" or "highsolubility tablet" form. Such product forms are free from abrasives. Theproduct of the process is preferably transparent, and, as describedelsewhere herein, may be both colored and perfumed.

Processing of Optional Ingredients

The present process and the product thereof allow for the presence of atleast one additional mixing step other than the essential minimum (a),(b), (c); wherein there is added an ingredient selected from the groupconsisting of surfactants, buffers, builders, chelants, perfumes,colorants, dyes, bleach stabilizers, pigments, suds supressors,anti-tamish and/or anti-corrosion agents, soil-suspending agents,germicides, alkalinity sources, hydrotropes, anti-oxidanta, clay soilremovavanti-redeposition agents, thickeners, solvents, and mixturesthereof. For other optional ingredients, see U.S. Pat. No. 3,583,922 orother references cited in the background, recognizing that '922 relatesto solid compositions as distinct from the liquids herein.

Other Ramifications

The present process can accomodate perfumes and colorants, mostparticularly known bleach-stable colorants such as various yellows; andperfumes offering citrus or pine character. Perfumes for use herein aredesirably hydrophobic, having relatively high octanol/water partitioncoefficients such as 6 or above. In process terms, it has been founddesirable to incorporate perfume in a step which follows (III) (a).Without being limited by theory, this is believed to be due to a reducedtendency for reaction of sulfamate derivatives with perfume aldehydeswhen they are incorporated late in the process. Also desirably,bleach-stable thickeners such as those referenced in background and/orLaponite®, a special day available from Laport, and/or fatty amineoxides may be combined using the present process to deliver producthaving a wide range of useful properties.

Optional Incredients in More Detail

Optional ingredients are now nonlimitingly illustrated in more detail.Such ingredients as noted include surfactants, bleach stabilizers,colorants, suds boosters, suds supressors, anti-tarnish and/oranti-corrosion agents, soil-suspending agents, germicides, alkalinitysources, hydrotropes, anti-oxidants, day soil removal/anti-redepositionagents, polymeric dispersing agents, and the like; and mixtures thereof.

The processes herein may make use of, based on the composition of theproduct, from about 0.1 % to about 95% of a surfactant or mixturesthereof selected from the group consisting of anionic, nonionic,ampholytic and zwitterionic surface active agents. For liquid systems,surfactant is preferably present to the extent of from about 0.1 % to20%, though higher levels, e.g., 30% are possible, for example inviscous gels, aqueous pastes or semi-solids.

Anionic surfactants herein can include water-soluble salts, particularlythe alkali metal salts, of C₈ -C₂₂ organic sulfuric reaction productsand a radical selected from the group consisting of sulfonic acid andsulfuric acid ester radicals. Sodium or potassium alkyl sulfates,especially those obtained by sulfating C₈ -C₁₈ alcohols are useful, asare linear or branched alkyl benzene sulfonates especially the C₉ -C₁₅alkyl-substituted sodium- or potassium- salt forms; also useful are thesodium alkyl glyceryl ether sulfonates, especially those ethers of thehigher alcohols derived from tallow and coconut oil; sodium coconut oilfatty acid monoglyceride sulfates and sulfonates; sodium or potassiumsalts of sulfuric acid esters of the reaction product of one mole of ahigher fatty alcohol (e.g. tallow or coconut alcohols) and about 1 toabout 10 moles of ethylene oxide; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates with about 1 to about 10 units ofethylene oxide per molecule and in which the alkyl radicals contain from8 to 12 carbon atoms; the reaction products of fatty acids derived fromcoconut oil sodium or potassium salts of fatty acid amides of a methyltauride in which the fatty acids, for example, are derived from coconutoil; and sodium or potassium beta-acetoxy- orbeta-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbonatoms.

Additionally, conventional primary alkyl sulfates, such as those havingthe general formula ROSO₃ ⁻ M⁺ wherein R is typically a linear C₈ -C₂₂hydrocarbon group and M is a water solublizing cation are useful herein,as are the secondary alkyl sulfates and/or branched chain primary alkylsulfate surfactants (i.e., branchd-chain "PAS") having 8-20 carbonatoms, see EP 439,316 A Smith et al. Secondary alkyl sulfate surfactantsinclude those materials which have the sulfate moiety distributedrandomly along the hydrocarbyl "backbone" of the molecule. Suchmaterials may be depicted by the structure

    CH.sub.3 (CH.sub.2).sub.n (CHOSO.sub.3.sup.- M.sup.+)(CH.sub.2).sub.m CH.sub.3

wherein m and n are integers of 2 or greater and the sum of m+n istypically about 9 to 17, and M is a water-solublizing cation.

In addition, the selected secondary (2,3) alkyl sulfate surfactants usedherein may comprise structures of formulas I and II

    CH.sub.3 (CH.sub.2).sub.x (CHOSO.sub.3.sup.- M.sup.+)CH.sub.3 I

    CH.sub.3 (CH.sub.2).sub.y (CHOSO.sub.3.sup.- M.sup.+)CH.sub.2 CH.sub.3 I

for the 2-sulfate and 3-sulfate, respectively. Mixtures of the 2- and3-sulfate can be used herein. In formulas I and II, x and (y+1) are,respectively, integers of at least about 6, and can range from about 7to about 20, preferably about 10 to about 16. M is a cation, such as analkali metal, ammonium, alkanolammonium, triethanol-ammonium, potassium,ammonium, and the like, can also be used.

The aforementioned secondary alkyl sulfates are those prepared by theaddition of H₂ SO₄ to olefins. A typical synthesis using alpha olefinsand sulfuric acid is disdosed in U.S. Pat. No. 3,234,258, Morris, issuedFeb. 8, 1996 or in U.S. Pat. No. 5,075,041, Lutz, issued Dec. 24, 1991.The synthesis conducted in solvents which afford the secondary (2,3)alkyl sulfates on cooling, yields products which, when purified toremove the unreacted materials, randomly sulfated materials, unsulfatedby-products such as C10 and higher alcohols, secondary olefinsulfonates, and the like, are typically 90+% pure mixtures of 2- and 3-sulfated materials (some sodium sulfate may be present) and are white,non tacky, apparently crystalline, solids. Some 2,3-disulfates may alsobe present, but generally comprise no more than 5% of the mixture ofsecondary (2,3) alkyl mono-sulfates. Such materials are available asunder the name "DAN", e.g., "DAN 200" from Shell Oil Company.

Especially preferred surfactants for use in the present process arethose having the highest possible bleach stability, including C₈ -C₂₂fatty amine oxides such as hexadecyidimethylamine N- oxide or saturatedfatty alkyl alkoxylates. Particularly objectionable surfactants arethose having a high degree of unsaturation, and any surfactantscomprising hypohalite-reactive nitrogen moieties. Somewhat lessproblematic, but still a potential source of difficulty, are the use ofany alcohols. Thus, when using alkyl ethoxylates, etc., the so-called"capped" forms in which terminal --OH is replaced by --OCH₃ or similarlyunreactive groups, is particularly preferred.

The most bleach-stable and hydrolytically-stable surfactants can beadded at various stages of the present process, but for convenience,their addition will generally be done in such manner as to minimizefoaming which may undesirably slow down the process. Silicone anti-foamsare desirable for limiting foam; such anti-foams are commerciallyavailable from Dow Corning Corp.

When processing a surfactant having susceptibility to acid hydrolysis,such as an alkyl sulfate, it is incorporated into the product in thepresent process at any point at which the pH of the mixture ofingredients has exceeded about 7, preferably, when said pH has exceededabout 8.

Although preferred processes and compositions herein are free frominsoluble materials and are non-abrasive, products of the presentprocess can be formulated in a solid or viscous semi-solid form furthercomprising an abrasive material, such as expanded perlite abrasive incombination with the surfactants, filler material, or other optionalscouring material ingredients listed herein. When desired, abrasivematerials can be those contained in U.S. Pat. No. 4,051,056, Hartman,issued Sep. 27, 1977.

Other optional ingredients to be used herein include buffers, forpurposes which include to adjust the cleaning surface pH to optimize thehard surface cleaner composition effectiveness relative to a particulartype of soil or stain. Buffers may also be included to stabilize theadjunct ingredients with respect to extended shelf life or for thepurpose of maintaining compatibility between various aestheticingredients. The hard surface cleaner of the present inventionoptionally contains buffers to help adjust and maintain the pH at about13 or in a range above about 13. Non-limiting examples of such suitablebuffers are potassium carbonate, sodium carbonate, and trisodiumphosphate, however, the formulator is not restricted to these examplesor combinations thereof.

The cleaning compositions obtainable according to the process of thepresent invention may also desirably be prepared with inclusion of aheavy metal ion control system, especially one comprising one or moreagents for the control of bleach destabilization caused by soluble,insoluble or colloidal iron and/or manganese and/or copper. A simple buteffective agent is sodium tripolyphosphate, optionally supported by atleast partially polymeric hydrous sodium silicate. Examples of otherchelating or heavy-metal control agents are phytic acid andethane-1-hydroxy-1,1-diphosphonic acid (EHDP), though other materials,such as a number of commercial phosphonate types, may be used. Preferredchelating agents herein, are free from alcohol sites, halogen-reactivenitrogen donor sites, and hydroltically sensitive sites. In processterms, a preferred addition of at least some chelating agent orheavy-metal ion control agent takes place at or near the beginning ofthe process, for example immediately before, or concurrent with, stepI(a). However, when adding a silicate for the purpose at least in partof helping control heavy metal ions, it is added at a point in theprocess which is remote from both the pH minimum and the pH maximum ofthe process

Perfumes when used are typically at levels of from 0% to 5%. See U.S.Pat. No. 4,246,129, Kacher, issued Jan. 20, 1981.

The compositions obtainable according to the process of the presentinvention typically have a yellow color. However, it is possible toprovide a preferred solution which has some other color, for example, bythe addition of a bleach-stable dye; moreover, preferred solutions mayreadily be diluted, in which case yellow color is difficult to detect.In process terms, dyes are preferably added at the end of the process,in which case product-making can be more conveniently monitored on acolorant-free product.

The liquid compositions obtainable according to the process of thepresent invention may be formulated with different viscosities. In oneembodiment of the present invention the compositions obtainable with theprocess herein have a viscosity of from about 1 to about 150 cps. Saidcompositions are convenient for spray bottle application. Likewise, saidliquid compositions obtainable according to the present invention can befurther thickened, e.g., by the addition of additional bleach-stablethickener, such as the commercially available DOWFAX. A suitable gelformulation has a viscosity of from about 100 cps to about 2000 cps,preferably from 300 cps to 1000 cps as measured, for example, bytechniques and methods described in "Physico-Chemical Methods", Reilly,J. and Rae, W. N.; Vol. 1 (5th ed.), pages 667-692; D. Van Nostran pub.Thickeners, when added in the instant process, are desirably used towardthe end of the process, for example, adding them immediately after, orconcurrent with, stage (III).

EXAMPLE 1

(I) Pre-Bromine Stage

All operations are conducted at ambient temperature, about 20° C. 30grams distilled water is placed in a chemically inert, plastic-linedreaction vessel. The vessel is set for operation at atmospheric pressureand as a precaution is connected to a scrubber for removing any minorquantity of chlorine vapors which might be emitted. The vessel isequipped with an inert-plastic-coated paddle stirrer. While stirring at300 rpm, 13.05 grams of aqueous sodium hypochlorite, assayed ascomprising 10.73% Available Chlorine, is added. Immediately thereafter,sulfamic acid (2.2 grams, Aldrich, 99.3%, crystalline) is added withcontinued stirring until the added solid has dissolved. At this point,the pH of the stage (I) mixture is about 1.0.

(II) Bromine Compound Addition Stage

To the stirred stage (I) mixture is added Sodium Bromide (0.5 grams, EMScience). The mixture is stirred until the added solid has dissolved(about 5 minutes) and a yellow color has appeared. The mixture at thispoint is identified as a Stage (II) mixture.

(III) Product Stabilization Stage

To the stirred stage (II) mixture is added Sodium Hydroxide (about 3.0grams, 50% in water) until the pH of the mixture is about 13.2. Water isadded until the total weight of the stage (III) mixture is about 100grams.

EXAMPLE II

The process of Example I is repeated with the following differences: Thescale of operations is increased 1000-fold. In a pre-processing step,chlorine gas is passed into sodium hydroxide solution, forming sodiumhypochlorite solution. The sodium hypochlorite solution is passed intothe above-identified reactor in batches, where it is treated withsulfamic acid, forming a stage (I) mixture. Steps subsequent to stage(I) are conducted in the manner of Example I.

EXAMPLE III

The process of Example II is repeated with the following difference:Sodium Sulfamate is substituted for sulfamic acid.

In the examples below, a heavy line indicates the boundary separatingStages (I), (II) and (III) of the process.

EXAMPLE IV

The process of Example III is repeated with the following difference:prior to completion of Stage I, aqueous hydrochloric acid is added toreduce the pH to about 7.0.

    ______________________________________                                        Ingredient        Addition Sequence                                                                          % wt                                           ______________________________________                                        Hydrous Sodium Silicate                                                                         (2)          0.20                                           (Britesil H2O, PQ Corp.)                                                      Sodium Tripolyphosphate                                                                                 (3)            0.20                                 First portion                                                                 Sodium Hypochlorite                                                                                         (4)                                                                                      0.90                                 Sulfamic Acid                            1.30                                 Potassium Bromide                        1.10                                 Sodium Tripolyphosphate                                                                                 (7)            7.60                                 Second Portion                                                                Sodium Hydroxide                         0.80                                 Cocodimethylamine N-Oxide                                                                             (9)              0.25                                 Dye                                  0.15    (10)                             Perfume                              0.60(11)                                 Water                          bal.        (1) and (12)                       ______________________________________                                                                       .                                               ("bal." means "balance to 100%")                                         

    ______________________________________                                        Ingredient      Addition Sequence                                                                          % wt                                             ______________________________________                                        Sodium Hypochlorite                                                                           (2)          1.4                                              Sulfamic Acid                             1.9                                 Sodium Silicate              (4)                                                                                     0.04                                   Sodium Bromide                            1.8                                 Sodium Hydroxide                                                                                          (6)                                                                                         1.6                                 Surfactant                                3.5                                 Dyes/perfume                           0.28                                   Water                                 bal. (9)                                ______________________________________                                         Note:                                                                         *"Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine NOxide or     a mixture thereof.                                                       

    ______________________________________                                        Ingredient      Addition Sequence                                                                          % wt                                             ______________________________________                                        Sodium Hypochlorite                                                                           (1)          1.4                                              Sodium Sulfamate/                                                                                        (2)                                                                                      2.2**                                   Sulfuric acid                                                                 Sodium Bromide                           1.5                                  Potassium Bromide                                                                                        (4)                                                                                         1.1                                  Sodium Silicate              (5)                                                                                    0.05                                    Perfume                                  0.1                                  Sodium Hydroxide                                                                                          (7)                                                                                        1.8                                  Sodium Octyl Sulfate                                                                                  (8)              5.5                                  Yellow Dye                            0.28                                    Water                                    bal.                                 ______________________________________                                         ("bal." means "balance to 100%")                                              **weight equivalent to sulfamic acid content, dry basis                  

    ______________________________________                                        Ingredient         Addition Sequence                                                                          wt %                                          ______________________________________                                        Cocodimethylamine N-oxide                                                                        (1)          3.0                                           Sodium Sulfamate/Sulfuric acid                                                                     (2)                  0.5**                               Calcium Hypochlorite                                                                                         (3)                                                                                      0.5                                 Sodium Dichlorocyanurate                                                                                 (4)            0.50                                Potassium Bromide                         1.5                                 Sodium Hydroxide                          0.8                                 Sodium Tripolyphosphate                                                                                   (7)           1.6                                 Sodium Acetate                            0.3                                 Potassium Hydroxide                                                                                           (9)                                                                                     0.85                                Sodium Octyl Sulfate                                                                                        (10)                                                                                      3.00                                Dyes/perfume                              0.28                                Water                                    bal.(12)                             ______________________________________                                         **weight equivalent to sulfamic acid content, dry basis                  

    ______________________________________                                        Ingredient        Addition Sequence                                                                          wt %                                           ______________________________________                                        Surfactant        (2)          6.1                                            Sodium Dichlorocyanurate                                                                               (3)                1.2                               Melamine                                    0.23                              Potassium Bromide                           1.0                               Tetrapotassium Pyrophosphate                                                                       (6)                   13.0                               Tripotassium Phosphate                                                                                   (7)             12.0                               Sodium Silicate                             0.5                               Calcium Carbonate                          39.0                               Calcium Oxide                           2.8                                   Perlite Abrasive                       22.5                                   Sodium Hydroxide                        1.1                                   Water                              bal. (1) and (13);                                                                   split 1:1 by weight                 ______________________________________                                         Note 1:                                                                       *"Surfactant" refers to C8 Alkyl Sulfate, C12-C14 Dimethylamine NOxide or     a mixture thereof.                                                       

What is claimed is:
 1. A process for manufacturing a bleaching composition comprising the steps of:a) admixing a source of hypohalite and an aminofunctional compound having the formula:

    RR'NH

wherein R and R' are independently hydrogen, an organic or inorganic unit, and mixtures thereof, provided both R and R' are not both hydrogen, to form a pre-bromine admixture having a pH not exceeding about 11; b) adding to the pre-bromine admixture a source of bromine to form a bromine addition admixture; and c) adjusting the pH of the bromine addition admixture to at least about 13 forming a bleaching composition.
 2. A process according to claim 1, wherein said aminofunctional compound is selected from the group consisting of:i) primary aminofunctional compounds selected from sulfamic acid, alkali metal sulfamates, alkaline earth sulfamates, terta-alkylammonium sulfamates, or mixtures thereof; ii) secondary amine derivatives having the formula:

    RR'NH or (R").sub.2 NH

wherein R, R', and R" are organic moieties and wherein carbon atoms of said moieties are bonded to NH; iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benzenesulfonamide, alkyl sulfonamides, or mixtures thereof; iv) melamine, cyanamide, or mixtures thereof; v) and mixtures thereof.
 3. A process according to claim 1, wherein said source of hypohalite in (a) is selected from the group consisting of chlorine gas, hypochlorous acid, alkali metal hypochlorites, alkaline earth metal hypochlorites, and mixtures thereof.
 4. A process according to claim 1 wherein said source of hypohalite in (a) is introduced by admixing a hypohalite-liberating compound with a source of aqueous alkali in the presence of the aminofunctional compound such that the final pH of the pre-bromine admixture does not exceed about
 11. 5. A process according to claim 1 wherein said source of bromine is selected from the group consisting of bromine, water-soluble bromide salts, water-soluble hypobromite salts, hypobromous acid, and mixtures thereof.
 6. A process according to claim 1 wherein the ratio of the number of moles of hypohalite added in (a) to the number of moles of aminofunctional compound added in (a) is from about 10:1 to about 1:10.
 7. A process according to claim 1 wherein the ratio of the number of moles of hypohalite added in (a) to the number of moles of said source of bromine added in (b) is from about 10:1 to about 1:10.
 8. A process according to claim 1 wherein steps (b) and (c) are conducted at a temperature of from about 5° C. to about 80° C.
 9. A process according to claim 1, wherein the pH of the pre-bromine admixture of step (a) is not in excess of about
 8. 10. A process according to claim 9 wherein the pH of the pre-bromine admixture of step (a) is from about 1 to about 6.9.
 11. A process according to claim 1 further comprising the step of adding to the bleaching composition formed in step (c) one or more carriers.
 12. A process according to claim 1 further comprising the step of adding to the bleaching composition formed in step (c) one or more adjunct ingredients, said adjunct ingredients selected form the group consisting of surfactants, buffers, builders, chelants, abrasives, perfumes, colorants, dyes, bleach stabilizers, pigments, color speckles, suds suppressors, anti-tarnish agents, anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal agents, anti-redeposition agents, thickeners, solvents, and mixtures thereof.
 13. A process according to claim 1 wherein said bleaching composition formed in step (c) has from about 0.01% to about 10% available chlorine.
 14. A process for manufacturing a bleaching composition comprising the steps of:a) admixing a source of hypohalite and an aminofunctional compound, at a temperature of from about 5° C. to about 80° C., to form a pre-bromine admixture having a pH not exceeding about 11; b) adding to the pre-bromine admixture, at a temperature of from about 5° C. to about 80° C., a source of bromine to form a bromine addition admixture; and c) adjusting the pH of the bromine addition admixture to at least about 13, at a temperature of from about 5° C. to about 80° C., to forming a bleaching composition.
 15. A process according to claim 14, wherein said aminofunctional compound is selected from the group consisting of:i) primary aminofunctional compounds selected from sulfamic acid, alkali metal sulfamates, alkaline earth sulfamates, terta-alkylammonium sulfamates, or mixtures thereof; ii) secondary amine derivatives having the formula:

    RR'NH or (R").sub.2 NH

wherein R, R', and R" are organic moieties and wherein carbon atoms of said moieties are bonded to NH; iii) sulfonamides selected from sulfamide, p-toluenesulfonamide, imidodisulfonamide, benzenesulfonamide, alkyl sulfonamides, or mixtures thereof; iv) melamine, cyanamide, or mixtures thereof; v) and mixtures thereof.
 16. A process according to claim 14, wherein said source of hypohalite in (a) is selected from the group consisting of chlorine gas, hypochlorous acid, alkali metal hypochlorites, alkaline earth metal hypochlorites, and mixtures thereof.
 17. A process according to claim 14 wherein said source of bromine is selected from the group consisting of bromine, water-soluble bromide salts, water-soluble hypobromite salts, hypobromous acid, and mixtures thereof.
 18. A process according to claim 14 further comprising the step of adding to the bleaching composition formed in step (c) one or more carriers or one or more adjunct ingredients, said adjunct ingredients selected form the group consisting of surfactants, buffers, builders, chelants, abrasives, perfumes, colorants, dyes, bleach stabilizers, pigments, color speckles, suds suppressors, anti-tarnish agents, anti-corrosion agents, soil-suspending agents, germicides, alkalinity sources, hydrotropes, anti-oxidants, clay soil removal agents, anti-redeposition agents, thickeners, solvents, and mixtures thereof.
 19. A process according to claim 14 wherein said bleaching composition formed in step (c) has from about 0.01% to about 10% available chlorine.
 20. A process for manufacturing a bleaching composition comprising the steps of:a) admixing a source of hypohalite, said source of hypohalite is selected from the group consisting of alkali metal hypochlorites, alkali earth metal hypochlorites, and mixtures thereof, and an aminofunctional compound, said amino compound selected from the group consisting of sulfamic acid, sulfamate salts thereof, and mixtures thereof, such that the ratio of the number of moles of hypohalite added to the number of moles of aminofunctional compound added is from about 10:1 to about 1:10, to form a pre-bromine admixture having a pH from about 1 to about 6.9; b) adding to the pre-bromine admixture a water-soluble bromide salt in an amount such that the ratio of the number of moles of hypohalite added in (a) to the number of moles of water-soluble salt added in (b) is from about 10:1 to about 1:10, to form a bromine addition admixture; c) adjusting the pH of the bromine addition admixture to at least about 13 forming a bleaching composition wherein said bleaching composition has from about 0.01% to about 10% available chlorine; d) optionally diluting said bleaching composition with a carrier; and e) optionally adding to said bleaching composition one or more adjunct ingredients. 